JPH01319523A - Production of stable low viscosity polymer polyol - Google Patents

Abstract

PURPOSE: To provide a low viscosity polymer polyol that can be forcedly fed in the uniform condition without generating separation of component and increase of viscosity at the time of storage, by filling a specified quantity of high molecular weight polyol dispersant so as to polymerize a base polyol and a monomer.

CONSTITUTION: (A) High molecular weight polyol at 6000 or more of molecular weight is filled in an reactor, and (B) a monomer, which is obtained by mixing (i) a base polyol at 4000 or more of molecular weight and (ii) styrene and acrylonitrille at 65/35-85/15 of mixture ratio, is added for reaction so as to obtain a target polyol, which includes the component A at 1-20% in relation to all the polyol.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the production of polymer polyols (polyhydric alcohols having polymer particles dispersed therein), and more particularly relates to the production of polymer polyols (polyhydric alcohols having polymer particles dispersed therein), and more particularly relates to the production of polymer polyols (polyhydric alcohols having polymer particles dispersed therein). This invention relates to a styrene/acrylonitrile (SAN) copolymer polyol in which the polyol is used as part of the dispersion medium (dispersant).

BACKGROUND OF THE INVENTION The use of polyols in the production of polyurethanes, ie, the reaction of polyols with polyisocyanates in the presence of catalysts and sometimes other ingredients, is well known in the art.

Polyols applied in the production of flexible polyurethane foams, such as slab urethane foams (relatively thick and wide plate-shaped urethane foams), have a molecular weight of about 2000 to 5000 or more. The alkylene oxide pathway is synthesized by reacting ethylene oxide or propylene oxide, or both ethylene oxide and propylene oxide, with a low molecular weight polyol. These polyols are reacted with polyisocyanes i in the presence of water or other blowing agents such as fluorocarbons.

The polyols used in the production of urethane foams have been modified in various ways to improve the properties of the polyurethane, such as by dispersing polymer particles in the polyol to form a polymer polyol. Ordinary polyols are
In these polymer polyols, it is used as the base polyol (dispersion medium).

As an example, polymers of vinyl compounds such as styrene or acrylonitrile or mixtures thereof (abbreviated as SAN monomers), or polyurea polymers made from toluene diisocyanate (D+) and hydrazine, dispersed in conventional polyols. Dispersions (polymeric polyols) are used to improve the properties of urethane foams. Polyurethane foams with high load carrying capacity (expressed as 1LD-indentation load value or CFD-compression load value) are produced using such polymer polyols.

To improve the properties of polyurethane foams, it is desirable to prepare stable and low viscosity polymer polyols. Stability is important for the shelf life of polyols for polyurethane foam production before use. Also, the low viscosity and small particle size of the polymer are important for easy pumping of high quality polyols in large volume film manufacturing equipment.

Acrylonitrile, high S A N ratio (styrene/acryloni 1
It would be more advantageous to be able to synthesize styrene/acrylonitrile polymer polyols (with a high proportion of styrene in the lyle copolymer). In these polymer polyols, lowering the proportion of acrylonitrile and instead increasing the proportion of sterone prevents deterioration during curing of the polyurethane and helps improve the flame retardancy of the resulting foam.

[Problem to be solved by the invention] However, the stability of the above polymer polyol is
It decreases as the styrene/acrylonitrile ratio increases. That is, the components tend to separate during storage, and properties such as viscosity and particle size of the polymer polyol deteriorate.

U.S. Pat. No. 4,119,586 to Shah uses a small amount (5-45% by weight) of a high molecular weight (HMW) polyol with an average molecular weight of 5000 or more, along with a major amount of a low molecular weight (LMW) polyol with a molecular weight of 4000 or less. Then,
It has been described that stable, low viscosity polymer polyols are obtained and relatively high polymer contents can be obtained. The upper limit for the molecular weight of LMW polyols is taught to be 4000. The minimum amount of H M W polyol found necessary is 5% of the total polyol, preferably 10%.
% or more.

Additionally, U.S. Patent Nos. 3,953,393 and 4,458,038
No. 2003-11-11, the critical apparent amount of unsaturated bonds or the specific composition of unsaturated polyols required.
In the presence of alkyl mercaptan as RN3 motive agent,
It has been described that polymer polyols with high styrene content can be produced by in situ polymerization.

However, the use of alkyl mercaptans in polyurethanes is undesirable because films made from these older materials have a bad odor. The odors of these chemicals and the foams produced therefrom make the foams difficult to use for both consumers and manufacturers.

The present invention has been made in view of the above, and its purpose is to provide a stable low-viscosity dispersion with a high styrene/acrylonitrile ratio (SAN ratio), for example, from about 50,750 to about 85/15. polymer polyol)
and a method for producing these dispersions.

[Means for Solving the Problems] In order to achieve the above-mentioned problems, the production method of the present invention includes a first step of charging a charge containing a high molecular weight polyol dispersant into a reactor; , a feed stream containing a pace polyol with a molecular weight greater than 4000, a monomer portion, and an initiator suitable for polymerizing the monomer portion, and an amount of the high molecular weight polyol dispersant; Total polyol (total polyol is defined as the total portion of high molecular weight polyol dispersant and base polyol) from about 1 to
This is a manufacturing method that keeps the amount within the range of 20%.

if necessary, charging the high molecular weight polyol dispersant into a first part and a second part, the first part into the reactor;
A second portion may be included in the feed stream. In this case, the combined amount of the first part and the second part of the high molecular weight polyol dispersant is about 1 to 20%, preferably 1 to 5% of the total polyol.
%.

Also, regarding the base monomer, the first part and the second part
The first portion may be charged to the reactor and the second portion may be contained in the feed stream.

The concentration of the high molecular weight polyol dispersant in the charge to the reactor is between 10 and 10% of the total polyol in the charge.
Preferably it is 0% by weight.

Reactors include batch reactors, semi-batch reactors and multiple continuous stirred tank reactors connected in series (CSTR
) is preferably used.

The high molecular weight polyol dispersant used in the present invention preferably has a molecular weight of more than 6,000, a functionality of 2 to 4, and preferably contains no derived unsaturated moieties. Specifically, a high molecular weight polyol synthesized by adding alkylene oxide to a polyfunctional initiator in the presence of zinc hexacyanocobaltate can be used as a dispersant.

Further, the monomer portion in the present invention is preferably a mixture of styrene and acrylonitrile, and more preferably the SAN ratio is 65/35 to 85/15.

[Function] Surprisingly, in the present invention, U.S. Pat.
Contrary to the teachings of US Pat. No. 9,586, base polyols of molecular weight greater than 4000 are used, and contrary to the teachings of the aforementioned US Pat. By using a method using a high molecular weight polyol dispersant, it is possible to produce a polymer polyol with low viscosity, stability, and a high SAN ratio.

In the present invention, the high molecular weight polyol dispersant used in an amount of 1 to 20% by weight based on the total polyol ratio helps in dispersing solid matter (polymer) produced by polymerization in a base polyol. It works to encourage. For this reason,
A polymer with a small particle size is uniformly dispersed in the base polyol, and a stable polymer polyol with low viscosity and whose components are difficult to separate during standing can be obtained.

Typical S A N ratios for conventional polymer polyols without high molecular weight polyol dispersants can range from no more than about 50,150 to 65/35. In contrast, the SAN ratio of the polymer polyol according to the present invention is between 50,150 and 9,515, more typically
Values as high as about 65/35 to 85/15 can be taken.

In addition, the weight percentage of 1,000 yen in the method of the present invention is
About 5-50%, more typically 15-40%.

Although batch reactors or semi-batch reactors are preferably used in the present invention, single continuously stirred tank reactors (CSTR) are completely unsuitable for carrying out the process of the present invention. Shah U.S. Pat. No. 4,119,586 uses a single +7) C3TR;
In the case of the present invention, it does not give good results. Multiple continuous stirred tanks connected in series provide a high proportion of polymeric polyol dispersant in the feed stream to the first C3TR and
The shift is such that the product at the TR is sent to the second C3TR and this second C3TR is also supplied with a feed stream.
Available for use. In order to realize the polymer polyol of the invention, it is important that a relatively high concentration of polymer polyol dispersant is initially charged to the reactor.

The polymer polyol of the present invention is conditioned at a temperature of 80-150°C, preferably about 100-130t. However, the reaction temperature is not particularly critical for carrying out the method of the invention.

The proportion of total polyol (high molecular weight polyol dispersant base polyol) in the feed stream ranges from 50 to 99% by weight, with the preferred proportion of total polyol in the feed stream being about 65 to 97% by weight; A particularly preferred proportion is 80-95% by weight.

The time of addition of the feed stream to the contents of the reactor is from 0.5 to 40 hours, preferably from 1 to 25 hours, although neither of these ranges is critical.

The proportion of initiator as a percentage by weight of the total reactants is 00
5 to 50% by weight, preferably 01 to 10% by weight.

According to one form of the invention, the pre-charge to the reactor may be entirely of high molecular weight polyol dispersant. Alternatively, the high molecular weight polyol dispersant may be diluted to a base polyol to dispersant ratio of 201 and charged to the reactor. Alternatively, the entire amount of the high molecular weight polyol dispersant may be added to the charge of the reactor, or as described above, a portion may be charged to the reactor and the remaining amount may be contained in the feed stream. It may also be supplied to the reactor.

The weight percentage of high molecular weight polyol dispersant in the total polyol component after completion of the feed stream addition to the reactor is approximately 1 to 2.
It is included in the range of 0% by weight. This ratio is preferably about 1
-10% by weight, more preferably 2-8% by weight,
2-5% by weight is particularly standard.

The base polyols of this invention are typically synthesized by reaction of an initiator containing multiple reactive hydrogens with one or more alkylene oxides.

Examples of suitable initiators include glycerin, alkanolamines, alkylamines, aryl or aromatic amines,
Sucrose, sorbitol, [・rimedylolbroban (TMP), α-methylglucosy[・, β-medylglucoside or other methyl glucosides, phenolic resins, anilines, mixed phenolic anilines, such as methyl nondianiline or bisphenol A, Mannich There are M compounds and mixtures thereof.

The base polyol can be made by alkoxylating an initiator with the desired number of moles of alkylene oxide. Preferably, the alkylene oxide has 2 to 4 carbon atoms and is therefore ethylene oxide, propylene oxide, butylene oxide or a mixture of these oxides. These oxides can be added to the initiator in combination or separately to form a block or cap. According to a preferred form, a mixture of ethylene oxide and propylene oxide is added to the initiator.

Alkoxylation can be carried out with or without a catalyst. KOH is a commonly used catalyst, but other catalysts may also be used.

The molecular weight of the base polyol is greater than 4000,
According to one form, it is 4000-6500, and according to another form, it is 4000-6000.

It is.

In the practice of this invention, the molecular weights of each of the high molecular weight dispersant and the base polyol cannot be the same. The molecular weight of the high molecular weight dispersant should be about 1500, preferably about 2000 greater than the molecular weight of the base polyol.

The high molecular weight polyol according to the invention preferably has a molecular weight of 6,000 or more, sometimes 10,000 or more, and a functionality of 2 to 4, preferably triols are used. The average functionality of the polymeric dispersants is about 3. The aforementioned initiators, along with others, are also used in the synthesis of high molecular weight polyol dispersants. As previously mentioned,
Random or block copolymers can be synthesized using well-known techniques by sequentially adding one or more alkylene oxides to a multivalent or multifunctional initiator, either together or separately.

Catalysts may be used, and a more or less preferred catalyst for high molecular weight polyol dispersants is a two-metal cyanide catalyst, particularly zinc hexacyanocobaltate, and the polyol used as a dispersant can be used herein by reference. No. 3,029,505, US Pat. No. 3,900,518, incorporated herein by reference.
No. 3941094 and No. 43551. It can be adjusted according to the method shown in No. O0. It has been found that low viscosity polymer polyols can be obtained when using high molecular weight polyol dispersants synthesized using zinc hexacyanocobaltate as a catalyst. Of course, other catalyst examples may be used, such as KOH.

Note that the average molecular weight of the polyol in this specification is a theoretical value (or an apparent value) calculated from the functionality and hydroxyl value. The true average molecular weight will be slightly less than this, depending on the degree of functionality below the original or theoretical functionality. Of course, to ensure a stable polymer polyol, the base polyol and the high molecular weight polyol dispersant should be matched in molecular weight to each other.

Preferred polymers used in the process of the invention are styrene and acrylonitrile to synthesize the copolymer, as described above. Styrene/acrylonitrile ratio (
SAN ratio) is as described above.

Other suitable compounds include butadiene, isoprene, 14-pentadiene, 16-hexadiene, 17-
Octadiene, styrene, acrylonitrile, methacriconyl-lyl, α-methylstyrene, styrenestyrene, 2,4-dimedylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, substituted such as cyanostyrene, phenylstyrene, cyclohexylstyrene, hensylstyrene Styrenes, such as substituted styrenes such as cyanostyrene, nitrostyrene, N,N-dimedylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, P-vinylsiphenylsulfite, P-vinylphenylphenyl oxide , acrylic monomers and substituted acrylic monomers, such as acrylic acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate-1., methyl methacrylate-1.
, cyclohexyl methacrylate, hensyl methacrylate, isopropyl methacrylate, octyl methacrylate, ethyl α-1-xyacrylate, methyl α
-acetaminoacrylate, butyl acrylate, 2
-Ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N,N-dimethylacrylamide, N,N-dihensyl acrylamide, N-butylacrylamide, methacrylformamide 1-, vinyl ester, vinyl ether, vinyl ketone, vinyl acetate, vinyl alcohol , vinyl butyrate, isopropynylacetate-1~, vinylpormate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl toluene, vinylnaphthalene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, Vinyl butyl ethyl, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3
．． 4-shihi1-1゜2-biran, 2-butoxy-2
゛-Vinyloxydiethyl ether, vinyl 2-ethyl mercabutoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, vinyl ethyl sulfite, vinyl ale sulfone, N-methyl-N-
Vinyl acetamide, N-vinylpyrrolitone, vinylnaphthalene, divinyl sulfite, divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate,
Methyl vinyl sulfonate, N-vinylpyrrole, dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, shimedylamitoethyl methacrylate, glycidyl acrylate ,
Acrylic alcohol, itaconic acid glycol monoester, vinyl pyridine, maleic anhydride, maleimide, N
-Substituted maleimide - Examples include, but are not limited to, N-phenylmaleimide.

The polymerization initiator catalyst may be any initiator suitable for the monomers used. Catalytic initiators useful in making the polymer polyol compositions of the present invention include:
Vinyl polymerization catalysts of the free radical type, such as peroxides, persulfates, perborates, percarbonates, azo compounds, etc. Specific examples include 2,2'-azobisisobutyronitrile (AIBN), cyisobrobyl peroxide carbonate, t
-butylperoxy-2-edylhexane-1, t-
butyl perbihalate, 2,5-dimethyl-hexane-
2,5-Seperu 2-ethylhexiny 1~, t-butylberneodecanoate, t-butylberhensoate, t-butylvercrotone-1, t-butylperisobutyrate, There is sheet t-butyl perphthalate 1-. Other suitable catalysts may of course also be used.

The manufacturing method of the wood invention and the polymer polyol will be explained in more detail below with reference to Examples.

[Example] The physical properties of polymer polyols in Examples were measured using the following measurement procedure.

Viscosity was measured using a Brookfield cone and plate viscosity system (spindle $CP-52, operating at 20 seconds - 1.25°C).

Particle size Measured using a Coulter N4 particle size analyzer using O-xyInon or isopropyl alcohol as a dispersion medium.

Centrifugeable solids (wt%) - Centrifuge the polymeric voliol zumble at 1470 radial centrifugal force "gw" at about 3300 rpm for about 24 hours, then invert the centrifuge tube for 4 hours. F+/
I turned on. The non-flowing cake at the bottom of the tube was recorded as the paddy weight of the sample tested.

The high molecular weight polyol dispersants used in the examples described below will be summarized and explained.

Dispersants 1-5 use zinc hexacyanocobaltate and are described in U.S. Pat.
No. 3,941,049 and No. 4,355,100 and contained relatively little unsaturation and no derived unsaturation. Dispersant 6 was also prepared using conventional techniques using OH as the catalyst and was relatively high in unsaturation. Dispersant 1~
Dispersant 3 had a molecular weight of about 10,000, Dispersant 4 had a molecular weight of about 8,000, and Dispersant 5 had a molecular weight of about 9,000.

Dispersant 1 Hydroxyl number 16, unsaturation amount o, o
It is a polyether of propylene oxide using glycerin as an initiator.

Dispersant 2 Hydroxyl number 16, unsaturation amount 0, 01
．． Omeq/g, and is a polyether of propylene oxide using glycerin as an initiator.

Dispersant 3 Hydroxyl number 16, unsaturation amount 0, 010m
eq/g, contains 15% ethylene oxide, and is a polyether of propylone oxide and ethylene oxide using glycerin as an initiator.

Dispersant 4 Hydroxyl number 19, unsaturation amount o, 01
．． 6 meq/g, contains 7% ethylene oxide, has an ethylene oxide cap, and is a polyether of propylene oxide using glycerin as an initiator.

Dispersant 5 Hydroxyl number 25, unsaturation amount 0, 013m
eq/g, contains 13% ethylene oxide, has an ethylene oxide gap, and is a polyether of propylene oxide using glycerin as an initiator.

Dispersant 6 Hydroxyl number 19, unsaturation amount 0, 09
7 meq/g, contains 13% ethylene oxide, has an ethylene oxide gap, and is a polyether of propynon oxide using glycerin as an initiator.

Examples 1-8 All polymer polyols in the non-examples were prepared according to the experimental procedures described below, unless otherwise specified.

First, a 3
A base polyol and a high molecular weight polyol dispersant were charged into a 1-pack 4-neck resin reactor in the specified amounts under nitrogen sludge. After heating the reactor charge to the reaction temperature, the feed or feed stream was then added over the indicated period of time to produce an opalescent polymer polyol. After the reaction is complete, keep the polymer polyol at the indicated room temperature for 05-10 hours (infiltration or aging time) and then string the reaction mixture at about 90-120'C at less than 5 mm Hg for 15-25 hours. The polymer polyol of Wood's invention was obtained.

Table 1 shows the production conditions of Examples 1 to 8 (Examples 2, 4, 5.6.8 Example 1 Example 1..3.7 Comparative Example) and the IJ4=fall of the obtained polymer polyol.

True〉-m=miichiman 2=-photograph=0
These examples demonstrate the effect of adding a high molecular weight polyol dispersant at various SAN ratios from 65/35 to 90/10. The molecular weights of all the dispersants were 6,000 or more as described above.

Comparing the same SAN ratios in Table 1, it can be seen that all polymer polyols within the scope of the present invention show improvements in low viscosity, increased stability, and decreased diameter. .

The base polyol used in all these examples was THA
NOL 5F-5505 (registered trademark molecular weight 4800,
08 value was 34).

Example 2 using 5% dispersant has the same SAN ratio of 5773.
Compared to Example 30, the viscosity is lower and the diameter of the ladle is smaller, but the difference between using and not using a dispersant becomes more obvious as the SAN ratio increases.

In Example 3 with a SAN ratio of 75/25 and no dispersant, the viscosity was unacceptably thick (6640 cps)
There are 299 solid substances with a particle size of 3 μm or more and which can be centrifuged. On the other hand, Example 4 using a dispersant at the same SAN ratio
-6, good polymer polyols were obtained.

In Example 7, which can be clearly contrasted with Example 8 with a SAN ratio of 85/15, no polymer polyol was produced (no polymer dispersed), but instead a two-phase system was produced. The polymer polyol of Example 8 had a low viscosity and a somewhat high amount of centrifugable solids.

Examples 9 to 18 The manufacturing conditions and properties of the polymer polyols of Examples 9 to 18 (Examples 10 to 12 and 15 to 18, Example 1, Examples 9, 13, and 14, and Comparative Examples) are shown in Table 2.

8〉's delicious fortune-telling. No. Sojiro = - Minoh81 1 part 00t -
-to'''Nth
” 02 horoscope of u2th. (to) 30
Memi-≧-120! To =
-8N8 u2 to ■
■Lotto = 8〉-Umama fortune-telling. Country Zero 1 8♀8♀8- a♀2 To
=
2nd floor = 2 8≧8ゎ8 fortune. , character l roroji8sho8
℃8=Isa=-Log1sun12 0';B-6Rro. G second yaw ≧-1
-Joy m mouth = = 8)-'s Mayuzumi divination 6- So 3 effects-≧-11 voices =
8sa = + FJ ++ N eye ” faction 88) -? Because of.
8, To:,''' Eye p 2■ 8) 50 Maro 6N Drink 1 Ro8-≧-j Yupi0!8-
+ end 80 These examples shown in Table 2 demonstrate the importance of adding the high molecular weight polyol dispersant to the reactor charge rather than the feed stream. That is, a half-hatch process is employed to maintain an initial high concentration of dispersant. Example 13. Addition of dispersant in the reactor charge/in the feed stream.
In No. 14, the viscosity, particle size and centrifugable male solids are increased. These examples 13.14 are most similar to the procedure used in the aforementioned US Pat. No. 41+,9586. The high molecular weight polyol dispersants used other than Example 15.16 were prepared using a zinc hexacyanocobaltate catalyst, and the dispersant of Example 1516 was prepared using KOH
It is prepared using a catalyst.

In all examples, the SAN ratio was 75/25. The molecular weight of the dispersant was in all cases greater than 6000. All polymer polyols within the scope of this invention have low viscosity, small particle size, and improved stability.

The pace polyol used in all these examples was THANOL 5F-5505 as in Examples 1-8.
Met.

In this case, too, no dispersant was used and in Example 9, a polymer polyol having undesirable properties was obtained compared to the polymer polymers of Examples 10-12 and 15-17. . The polymer polyol 4J obtained in Example 18 had a slightly higher viscosity than that of Example 9 (viscosity/strength) and smaller particle size.

Examples 19-23 The manufacturing conditions of Examples 19-23 and the properties of the resulting polymer polyols are shown in Table 3.

Examples 19 to 23 are examples in which different pace polyols were used. In all these examples, the molecular weight is 4800 (
7) ARCOLI 342® was used as the pace polyol. The SAN ratio was set to 75/25.

Also in this case, Example 21 using a high molecular weight polyol dispersant
, 22.23 had favorable properties compared to the polymer polyol of Example 19.20 in which no dispersant was used.

The polymer polyols prepared according to each side mentioned above were
Polyurethane can be incorporated into the resulting formulation. The polymer polyols of the present invention can be used with the polyisocyanates described above, or can be reacted with polyisocyanates in combination with other polyols well known in the art to form polyurethane film products.

Catalysts useful in the preparation of this type of foam are used in accordance with conventional methods to form the BoI/tanf sub-me. In addition to the above-mentioned catalysts, there are also
Amines, tertiary bosphines, strong bases such as hydroxides, alkoxides and phenoxides of alkali and alkaline earth metals, acidic metal salts of strong acids, salts of various metals, alkola-1 and phenolates of various metals. , salts of organic acids and various metals, tetravalent, trivalent and pentavalent AS, Sb.

One or more of the organometallic derivatives of B1 and metal carbonyls of iron and cobalt may be present.

Of course, any combination of the catalysts for polyurethane production described above may also be used. The usual amount of catalyst used is polyol 1
001 to 50 parts by weight. The amount of catalyst used in most cases is between 0.2 and 20
Parts by weight.

As is well known, the polyol component of the polyurethane foam is reacted with polyisocyanate-1. in the presence of one or more of the aforementioned catalysts according to known procedures. As polyisocyanates, aromatic or aliphatic polyisocyanates can be used.

Foaming is carried out in the presence of water and sometimes an organic blowing agent. The amount of water is 05 to 15 parts by weight, preferably 10 to 10 parts by weight, per 100 parts by weight of polymer polyol and added polyol. Organic blowing agents optionally used with water are known in the art and are monofluorotrichloromethane, difluorodichloromethane, methylene dichloride and other materials well known in the art. Additives to control cell size and structure, such as silicone surfactants such as dimethylpolysiloxane, can also be added to the foaming mixture.

Fillers, flame retardants, paints or plasticizers of known type may be used. These as well as other additives are well known to those skilled in the art. Details regarding the preparation of polyurethane foams are provided in U.S. Patent No. 197,938.

From the above examples and comparative examples, it is clear that in the synthesis of polymer polyols containing SAN polymers, molecular weight
By using a base polyol larger than 85/
It is clear that higher SAN weight ratios of up to 15, higher contents of dispersed polymer solids and lower viscosities can be achieved. The use of semi-batch reactors with a relatively high concentration of dispersant initially charged to the reactor also
Helps in achieving favorable results. Moreover, the use of high molecular weight polyol dispersants to obtain these good results is
The amount may be as small as 5% or less.

Various modifications can be made to the polymer polyol according to the present invention and the method for producing the same without departing from the scope of the present invention. For example, one skilled in the art will appreciate that the temperature, pressure, reactants,
The ratio and mode of addition can be adjusted arbitrarily within the parameters mentioned above.

Description of the product used *ARCOL +342 (registered trademark) A polyether of propylene oxide and ethylene oxide using trilodylolpropane as an initiator. Edylene oxide content approximately 14%, hydroxyl value 0.35, primary hydroxyl group content 75-8
0% (based on the total hydroxyl content of the polyether).

*THANOL 5F-5505 (Registered business license
) Polyether of propylene oxide and ethylene oxide using glycerin as an initiator. Ethylene oxide content: approximately 20%, hydroxyl number: 34, primary hydroxyl group content: 80% (based on total hydroxyl content of polyether *Vaz○ (Hashi) 67 E I, 2,2゛-Asobis(2-methylbutane) manufactured by DuPont) Nitrile) polymerization catalyst.

[Effect of the invention] As mentioned above, in the present invention, the molecular weight is 4000 or more.
By using the second base polyol and a high molecular weight polyol dispersant, the particle size of the polymer dispersed in the base polyol is small, has a low viscosity, and is stable.
Polymer polyols can be produced.

Further, according to the present invention, the styrene/acrylonitrile ratio of the polymer can be increased while maintaining the excellent stability of the polymer polyol, and such a polymer polyol can be used to produce a highly flame-retardant polyurethane foam. Something will happen.

In general, in the present invention, since substances such as alkyl mercaptans are not used to increase the methylone/acrylonitrile ratio, there is no problem of bad odor.

The polymer polyol of the present invention does not separate its components or thicken during storage, and can be easily pumped in a uniform state. Suitable for producing polyurethane foam.

Agent: Patent Attorney Tadashi Sato

Claims (1)

[Scope of Claims] (1) A step of charging a charge containing a high molecular weight polyol dispersant into a reactor; providing a feed stream containing an initiator suitable for polymerization, and wherein the amount of the high molecular weight polyol dispersant is in the range of about 1-20% of the total polyol. Method for producing polymer polyol. (2) The molecular weight of the high molecular weight polyol dispersant is about 60
2. The method of claim 1, wherein the polymer polyol has a functionality of greater than 0.00 and a functionality of about 2 to 4. (3) a high molecular weight polyol dispersant in the charge charged to the reactor is a first portion of the dispersant, and a second portion of the high molecular weight polyol dispersant is contained in the feed stream; ,
2. The method of producing a polymer polyol according to claim 1, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is within the range of about 1 to 20% of the total amount of all polyols. (4) The method for producing a polymer polyol according to claim 1, wherein the monomer portion is a styrene/acrylonitrile mixture having a styrene/acrylonitrile ratio of about 50/50 to 95/5. (5) The method for producing a polymer polyol according to claim 1, wherein the monomer portion is a styrene/acrylonitrile mixture having a styrene/acrylonitrile ratio of about 65/35 to 85/15. (6) The concentration of the high molecular weight polyol dispersant in the charge charged to the reactor is 10 to 1% of the total polyol in the charge.
The method for producing a polymer polyol according to claim 1, wherein the content is in the range of 0.00% by weight. (7) The reactor may include a batch reactor, a semi-batch reactor, and a plurality of continuous stirred tank reactors (CS) connected in series.
2. A process for producing a polymer polyol according to claim 1, wherein the reactor is selected from the group consisting of: TR). (8) The first part and the second part of the high molecular weight polyol dispersant.
4. The method for producing a polymer polyol according to claim 3, wherein the total amount of the polymer polyol is in the range of about 1 to 5% of the total amount of all polyols. (9) The first part and the second part of the high molecular weight polyol dispersant
4. The method of claim 3, wherein the total amount of the polymer polyol is in the range of about 1 to 3% of the total amount of all polyols. (10) The method for producing a polymer polyol according to claim 3, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is in the range of about 1 to 2% of the total amount of all polyols. (11) The viscosity of the resulting polymer polyol is approximately 500
2. The method for producing a polymer polyol according to claim 1, which has a polyol having a polyol of less than 0 CPS. (12) The method for producing a polymer polyol according to claim 1, wherein the high molecular weight polyol dispersant is synthesized by adding alkylene oxide to a polyfunctional initiator in the presence of zinc hexacyanocobaltate. (13) The ratio of total polyols in the feed stream is 50 to 9.
A method for producing a polymer polyol according to claim 1, wherein the content is in the range of 9% by weight. (14) In the charge charged to the reactor, the molecular weight is 4.
2. The method for producing a polymer polyol according to claim 1, wherein the base polyol is greater than 0.000. (15) The molecular weight of the high molecular weight polyol dispersant is about 6.
15. The method for producing a polymer polyol according to claim 14, wherein the polymer polyol has a functionality of greater than 000 and a functionality of about 2 to 4. (16) a high molecular weight polyol dispersant in the charge charged to the reactor is a first portion of the dispersant, and a second portion of the high molecular weight polyol dispersant is contained in the feed stream; and the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is within the range of about 1 to 20% of the total amount of all polyols. (17) The method for producing a polyol according to claim 14, wherein the monomer portion is a styrene/acrylonitrile mixture having a styrene/acrylonitrile ratio of about 50/50 to 95/5. (18) The method for producing a polymer polyol according to claim 14, wherein the monomer portion is a styrene/acrylonitrile mixture having a styrene/acrylonitrile ratio of about 65/35 to 85/15. (19) The amount of high molecular weight polyol dispersant in the charge charged to the reactor is 10 to 5% of the total polyol in the charge.
The method for producing a polymer polyol according to claim 14, wherein the content is in the range of 0% by weight. (20) The reactor may include a batch reactor, a semi-batch reactor, and a plurality of continuous stirred tank reactors connected in series (C
Claim 1 selected from the group of reactors consisting of STR)
4. The method for producing a polymer polyol according to 4. (21) The method for producing a polymer polyol according to claim 16, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is in the range of about 1 to 5% of the total amount of all polyols. (22) The method for producing a polymer polyol according to claim 16, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant ranges from about 1 to 3% of the total amount of all polyols. (23) The method for producing a polymer polyol according to claim 16, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is in the range of about 1 to 2% of the total amount of all polyols. (24) The viscosity of the resulting polymer polyol is approximately 500
15. The method for producing a polymer polyol according to claim 14, wherein the polyol has a lower CPS. (25) The method for producing a polymer polyol according to claim 14, wherein the high molecular weight polyol dispersant is synthesized by adding alkylene oxide to a polyfunctional initiator in the presence of zinc hexacyanocobaltate. (26) The ratio of total polyols in the feed stream is 50 to 9.
15. The method for producing a polymer polyol according to claim 14, wherein the content is in the range of 9% by weight. (27) The method for producing a polymer polyol according to claim 14, wherein the base polyol in the charge charged to the reactor and the base polyol being fed are the same polyol. (28) charging a reactor with a charge comprising a high molecular weight polyol dispersant having a molecular weight greater than about 6000; supplying a feed stream containing a suitable initiator to polymerize the monomer portion, and wherein the amount of the high molecular weight polyol dispersant is in the range of about 1-5% of the total polyol. A method for producing a viscous polymer polyol. (29) The method for producing a polymer polyol according to claim 28, wherein the high molecular weight polyol dispersant does not contain an induced unsaturated moiety. (30) The method for producing a polymer polyol according to claim 28, wherein the monomer portion is a styrene/acrylonitrile mixture having a styrene/acrylonitrile ratio of about 65/35 to 85/15. (31) The amount of high molecular weight polyol dispersant in the charge charged to the reactor is 10 to 10% of the total polyol in the charge.
29. The method for producing a polymer polyol according to claim 28, wherein the content is in the range of 100% by weight. (32) The reactor may include a batch reactor, a semi-batch reactor, and a plurality of continuous stirred tank reactors connected in series (C
Claim 2 selected from the group of reactors consisting of STR)
8. The method for producing a polymer polyol according to 8. (33) a high molecular weight polyol dispersant in the charge charged to the reactor is a first portion of the dispersant, a second portion of high molecular weight polyol is contained in the feed stream, and 29. The method of making a polymer polyol according to claim 28, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant ranges from about 1 to 3% of the total amount of all polyols. (34) The method for producing a polymer polyol according to claim 33, wherein the total amount of the first portion and the second portion of the high molecular weight polyol is within the range of about 1 to 2% of the total amount of all polyols. (35) In the charge charged to the reactor, the molecular weight is 4.
29. The method for producing a polymer polyol according to claim 28, wherein the base polyol is greater than 000. (36) The method for producing a polymer polyol according to claim 33, wherein the base polyol in the charge charged to the reactor and the base polyol in the feed stream are the same polyol. (37) A charge comprising a first portion of a high molecular weight polyol dispersant having a molecular weight greater than about 6,000 and containing no derived unsaturation and a first portion of a base polyol having a molecular weight greater than 4,000. charging a reactor with a second portion of the high molecular weight polyol dispersant, a second portion of the base polyol, a monomer portion, and a material suitable for polymerizing the monomer portion. and providing a feed stream comprising an initiator, and the amount of the first portion of high molecular weight polyol dispersant in the charge is in the range of 10 to 50% of the total polyol in the charge. and a method for producing a stable low molecular weight polymer polyol, wherein the total amount of the first part and the second part of the high molecular weight polyol dispersant is in the range of about 1 to 5% of the total amount of all polyols. (38) The method for producing a polymer polyol according to claim 37, wherein the monomer portion is a mixture of styrene and acrylonitrile with a styrene/acrylonitrile ratio of 65/35 to 85/15. (39) The reactor may include a batch reactor, a semi-batch reactor, and a plurality of continuous stirred tank reactors connected in series (C
Claim 3 selected from the group of reactors consisting of STR)
7. The method for producing a polymer polyol according to 7. (40) The method for producing a polymer polyol according to claim 37, wherein the total amount of the first portion and the second portion of the high molecular weight polyol dispersant is in the range of about 1 to 2% of the total amount of all polyols. (41) A step of charging a charge containing a high molecular weight polyol dispersant into a batch reactor, and polymerizing a base polyol having a molecular weight greater than 4000, a monomer portion, and the monomer portion into the batch reactor. and providing a feed stream containing a suitable initiator, and wherein the high molecular weight polyol dispersant is in the range of about 1 to 20% of the total amount of all polyols. Viscous polymer polyol. 42. The stable low viscosity polymer polyol of claim 41, wherein said base polyol is free of derived unsaturated compounds. 43. The stable, low viscosity polymer polyol of claim 41, wherein the monomer portion is a mixture of styrene and acrylonitrile with a styrene/acrylonitrile ratio of about 50/50 to 95/5. 44. The stable, low viscosity polymer polyol of claim 41, wherein the monomer portion is a mixture of styrene and acrylonitrile with a styrene/acrylonitrile ratio of about 65/35 to 85/15. (45) Claim 41: The viscosity is lower than about 5000 CPS.
Stable, low viscosity polymer polyols as described. (46) In the charge charged to the reactor, the molecular weight is 4.
42. The stable, low viscosity polymer polyol of claim 41 obtained by a process which also includes a base polyol greater than 0.000. (47) The stable low-viscosity polymer polyol according to claim 46, obtained by a production method in which the base polyol in the charge charged to the reactor and the base polyol in the feed stream are the same polyol. . (48) A step of charging a charge containing a high molecular weight polyol dispersant into a batch reactor, and polymerizing a base polyol having a molecular weight of more than 4000, a monomer portion, and the monomer portion into the batch reactor. and supplying a feed stream containing an initiator suitable for the production of polymers, wherein the amount of the high molecular weight polyol dispersant ranges from about 1 to 20% of the total amount of all polyols. A polyurethane product manufactured by reacting a polyol with an organic polyisocyanate in the presence of a catalyst.